This invention relates to a porous crystalline synthetic material constituted by silicon and titanium oxides, a method for synthesizing said material, and the use thereof as a catalyst.
Said material is given the name titanium silicalite or TS-1, and corresponds to the following formula:
xTiO2.(1-x)SiO2
where x lies between 0.0005 and 0.04, preferably between 0.01 and 0.025.
The material is prepared starting from a mixture constituted by a source of silicon oxide and a source of titanium oxide. The reaction takes place in the aqueous phase at a temperature of 130° to 200°C, and the solid product obtained is calcined in air at 550°C
The TS-1 can be used for alkylation of toluene with methanol, or benzene with ethylene or ethanol, disproportioning of toluene to produce paraxylol, for cracking, hydrocracking, isomerization of n-paraffins and naphthenes, reforming, isomerization of substituted polyalkyl aromatics, disproportioning of aromatics, conversion of dimethylether and/or methanol or other alcohols to hydrocarbons, polymerization of compounds containing olefine or acetylene bonds, conversion of aliphatic carbonyl compounds into at least partly aromatic hydrocarbons, separation of ethyl benzene from other C8 aromatic hydrocarbons, hydrogenation and dehydrogenation of hydrocarbons, methanation, oxidation, dehydration of aliphatic compounds containing oxygen, and conversion of olefines into compounds of high octane number.
|
1. The method of preparing a porous, crystalline material comprised of silicon oxide and titanium oxide wherein the ratio of said oxides is represented by the formula
xTiO2.(1-x)SiO2 in which x is a number between 0.0005 and 0.04, which comprises the steps of: (1) preparing an aqueous mixture of starting reagents free from alkali- and alkaline-earth metals including a source of silicon oxide selected from the group consisting of silica gel and tetraalkylorthosilicates, a source of titanium oxide consisting of a hydrolysable titanium compound, and a nitrogenated organic base, and wherein the starting reagents have the following molar ratios: SiO2 /TiO2 from 5 to 200, OH- /SiO2 from 0.1 to 1.0, H2 O/SiO2 from 20 to 200, RN+ /SiO2 from 0.1 to 2.0 wherein RN+ is the cation of the nitrogenated organic base, (2) subjecting said mixture to hydrothermal treatment in an autoclave at a temperature in the range of 130° to 200° centrigrade under its own pressure for a period of 6 to 30 days to obtain crystals and a mother liquor, (3) separating said crystals from the mother liquor, (4) washing the separated crystals with water and then drying the same, and (5) heating the dried crystals in air so as to calcine the same and eliminate said nitrogenated base therefrom. 2. A method as claimed in
3. A method as claimed in
4. A method as claimed in
5. A method as claimed in
6. A method as claimed in
7. A method as claimed in
SiO2 /TiO2 from 35 to 65, OH- /SiO2 from 0.03 to 0.6, H2 O/SiO2 from 60 to 100, RN+ /SiO2 from 0.4 to 1∅
|
This is a continuation of application Ser. No. 208,420, filed Nov. 19, 1980, now abandoned.
This invention relates to a porous crystalline synthetic material constituted by silicon and titanium oxides, a method for its preparation, and its uses.
Hereinafter in the description, said synthetic material will be known as titanium silicalite, or more briefly TS-1. U.S. Pat. No. 3,329,481 describes zeolites containing titanium, which are prepared from siliceous materials and inorganic titanium compounds in the absence of organic bases. "Silicalite", a zeolite structure constituted by pure crystalline SiO2, has been described by Flanigen E. M. and others (Nature 271, 512 (1978)).
A crystalline porous silica having a structure of silicalite type in which the titanium is mentioned, among many other metals, as modifier, is described in the U.S. patent appln. Ser. No. 46,923 filed on June 8, 1979.
The same patent application describes an embodiment in which the amount of titanium is about 3.11 mol % with respect to the silica.
Within the composition range of 0.0001-1 TiO2.1 SiO2 described in the aforesaid patent application, a composition range has now been found which enables a titanium silicalite to be obtained having surprising catalytic properties in those reactions in which said catalysts are used.
The composition range of the titanium silicalite according to the present invention, expressed in terms of molar reagent ratios, is as follows:
______________________________________ |
Molar reagent ratio |
Preferably |
______________________________________ |
SiO2 /TiO2 |
5-200 35-65 |
OH- /SiO2 |
0.1-1.0 0.3-0.6 |
H2 O/SiO2 |
20-200 60-100 |
Me/SiO2 0.0-0.5 0 |
RN+ /SiO2 |
0.1-2.0 0.4-1.0 |
______________________________________ |
RN+ indicates the nitrogenated organic cation deriving from the organic base use for preparing the titanium silicalite according to the invention.
Me is an alkaline ion, preferably Na or K.
The final TS-1 has a composition corresponding to the formula xTiO2.(1-x)SiO2, where x lies between 0.0001 and 0.04, preferably between 0.01 and 0.025. The TS-1 is of the silicalite type, and all the titanium substitutes the silicon. The synthetic material according to the invention has characteristics which are demonstrated by a X-ray and infrared examination.
The X-ray examination is carried out by means of a powder diffractometer provided with an electronic pulse counting system, using CuKα- radiation. The products according to the present invention are characterised by an X-ray diffraction spectrum as shown in FIG. 1b. This spectrum is similar overall to the typical silicalite spectrum (FIG. 1a), however it comprises some clearly "single" reflections where evident double reflections are present in the pure silicalite spectrum. As the spectral differences between TS-1 and silicalite are relatively small, particular care is required in the spectral determination. For this reason, TS-1 and silicalite were examined by the same apparatus using αAl2 O3 as the internal standard.
Table 1 shows the most significant spectral data for a TS-1 with x=0.017, and a pure silicalite.
The elementary crystalline cell constants were determined by the method of minimum squares, on the basis of the interplanar distances of 7-8 single reflections within the range of 10°-40° for 2θ.
A large proportion of the interplanar distances for the TS-1 are, even though slightly, tendentially greater than the corresponding distances for the pure silicalite, in accordance with the higher foreseeable value of the Ti--O bond distance with respect to that of the Si--O bond distance.
Passage from double reflection to a single reflection is interpreted as a change from a monoclinic symmetry (pseudo orthorhombic) (silicalite) to an effective orthorhombic symmetry (titanium silicalite (TS-1)). The arrows in FIGS. 1a and 1b indicate the more apparent of the aforegoing spectral differences.
Passage from the monoclinic structure (silicalite) to the orthorhombic structure takes place above a titanium concentration of the order of 1%.
However, both the elementary cell volume and the intensity of a characteristic IR absorption band (see hereinafter) clearly demonstrate the continuity of the substitution phenomenon (see FIGS. 3a and 3b).
TS-1 shows a characteristic absorption band at about 950 cm-1 (see FIG. 2, spectra B, C and D) which is not present in the pure silicalite spectrum (FIG. 2, spectrum A), and is absent in titanium oxides (rutile, anatase) and in the alkaline titanates.
Spectrum B is that of the TS-1 containing 5 mol % of TiO2. Spectrum C is that of the TS-1 containing 8 mol % of TiO2. Finally, spectrum D is that of the TS-1 containing 2.3 mol % of TiO2.
As can be seen from FIG. 2, the intensity of the band at about 950 cm-1 increases with the quantity of titanium which substitutes the silicon in the silicalite structure.
In morphological terms, TS-1 is in the form of parallelepipeds with rounded edges. A X-ray microprobe examination has demonstrated that the titanium distribution within the crystal is perfectly uniform, thus confirming that the titanium substitutes the silicon in the silicalite structure, and is not present in other forms.
The adsorption isotherm determined by the BET method with O2 shows that TS-1 has the typical behaviour of a molecular sieve with a pore volume saturation capacity of 0.16-0.18 cm3 g-1.
This property makes TS-1 suitable for use as an adsorbent with hydrophobic characteristics.
The chemical and catalytic properties of TS-1 can be modified by introducing other substituting elements such as B, Al, Fe etc. during the synthesis stage.
The present invention also relates to a method for preparing the synthetic material constituted by silicon and titanium oxides.
In the aforesaid patent application is described a method for preparing a silicon and titanium oxide-based material using 30% hydrogen peroxide solution to allow solubilisation of the titanium compounds in a basic environment.
It has been found that the addition of the hydrogen peroxide solution is not necessary under certain conditions, and thus the preparation method for the material according to the invention is greatly simplified.
The method for preparing TS-1 comprises the preparation of a reaction mixture constituted by sources of silicon oxide and titanium oxide, and possibly an alkaline oxide, a nitrogenated organic base and water, having a reagent molar ratio composition as heretofore defined.
The silicon oxide source can be a tetraalkylorthosilicate, preferably tetraethylorthosilicate, or simply a silica in colloidal form, or again a silicate of an alkaline metal, preferably Na or K.
The titanium oxide source is a hydrolysable titanium compound chosen preferably from TiCl4, TiOCl2, and Ti(alkoxy)4, preferably Ti(OC2 H5)4.
The organic base is a tetraalkylammonium hydroxide, in particular tetrapropylammonium hydroxide.
The reagent mixture is subjected to hydrothermal treatment in an autoclave at a temperature of between 130° and 200°C, under its own pressure, for a time of 6-30 days until the crystals of the TS-1 precursor are formed. These are separated from the mother solution, carefully washed with water and dried.
In the anhydrous state they have the following composition: xTiO2.(1-x)SiO2.∼0.04(RN+)2 O. The precursor crystals are heated for 1 to 72 hours in air at 550°C in order to completely eliminate the nitrogenated organic base. The final TS-1 has the composition: xTiO2.(1-x)SiO2 where x is as heretofore defined. Chemical-physical examinations are carried out on the products thus obtained. The uses of the titanium silicalite according to the invention are in particular the following:
(1) alkylation of benzene with ethylene or ethanol, and alkylation of toluene with methanol
(2) disproportioning of toluene to produce paraxylol
(3) cracking and hydrocracking
(4) isomerisation of n-paraffins and naphthenes
(5) reforming
(6) isomerisation of substituted polyalkyl aromatics
(7) disproportioning of aromatics
(8) conversion of dimethylether and/or methanol or other low molecular weight alcohols into hydrocarbons
(9) polymerisation of compounds which contain olefine or acetylene bonds
(10) conversion of aliphatic carbonyl compounds into at least partly aromatic hydrocarbons
(11) separation of ethylbenzene from other aromatic C8 hydrocarbons
(12) hydrogenation and dehydrogenation of hydrocarbons
(13) methanation
(14) oxidation
(15) dehydration of aliphatic compounds containing oxygen
(16) conversion of olefines into compounds of high octane number.
Some examples are given hereinafter in order to better illustrate the invention, but without limiting it in any way.
This example illustrates the preparation of TS-1 with a high degree of purity.
455 g of tetraethylorthosilicate are placed in a pyrex glass vessel fitted with a stirrer and kept under a CO2 -free atmosphere, and 15 g of tetraethyltitanate are added followed gradually by 800 g of a 25% weight solution of tetrapropylammonium hydroxide (free from inorganic alkali). The mixture is kept stirred for about one hour, then heating is commenced carefully in order to accelerate hydrolysis and evaporate the ethyl alcohol which is released.
After about 5 hours at 80°-90°C, the alcohol has been completely eliminated. The volume is increased to 1.5 liters with distilled water, and the opalescent homogeneous solution is transferred to a titanium autoclave fitted with a stirrer. The mixture is heated to 175°C, and is kept stirred at this temperature under its own pressure for a time of ten days. When the treatment is finished, the autoclave is cooled, the contents are discharged, and the mass of fine crystals obtained is recovered. This is carefully washed on a filter with hot distilled water many times.
The product is then dried and finally calcined at 550°C for six hours.
The X-ray diffraction spectrum for the calcined product corresponds to that of the TS-1 given in FIG. 1b and Table 1.
This example illustrates the preparation of TS-1 using tetrapropylammonium peroxytitanate as the titanium oxide source.
The pertitanates are known to be stable in a strongly basic solution.
150 g of tetraethyltitanate are hydrolysed by slowly dripping into 2.5 liters of distilled water under stirring. A white gelatinous suspension is obtained. It is cooled to 5°C and 1.8 liters of 30% hydrogen peroxide, also cooled to 5°C, are added, then stirring occasionally over two hours while maintaining the temperature low. A clear orange-coloured solution is obtained. At this point, 2.4 liters of a 25% aqueous tetrapropylammonium hydroxide solution pre-cooled to 5°C are added. After one hour, 500 g of Ludox colloidal silica containing 40% of SiO2 are added, mixing is carried out carefully, and the mixture left standing overnight at ambient temperature. It is finally heated under stirring to 70°-80°C for 6-7 hours. The mixture thus obtained is transferred to an autoclave, and the operations described in example 1 are then carried out.
The final product when under X-ray examination is found to be properly crystallised pure TS-1.
Operating under the conditions described in example 2, five preparations were made in which the molar ratios of the reagents (expressed as SiO2 /TiO2) and the tetrapropylammonium quantity (expressed as RN+ /SiO2) were varied. The results of the chemical analysis, the variation in lattice volume and the IR absorbency ratio for the bands at 950 cm-1 (Ti) and at 800 cm-1 (Si) are summarised in table 2.
FIGS. 3a and 3b show respectively the variation of the ratio between the intensities of the IR absorption bands and the variation of the lattice volumes.
The abscissa in this figures represents the content x of TiO2 expressed in mol %.
The point O on the abscissa corresponds to the aforesaid values for pure silicalite. The approximately linear variation of both the aforesaid quantities as the titanium concentration varies can be seen.
This example illustrates how the acid properties of TS-1 are considerably influenced by the introduction of traces of aluminum.
Operating exactly as in example 2, 4.27 g of NaAlO2 were previously added to the 500 g of Ludox colloidal silica (molar reagent ratio SiO2 /Al2 O3 =128). Although the TS-1 obtained does not show appreciable differences under X-ray examination from that obtained in example 2, it shows in the H+ form a considerably increased acidity (passing from a concentration of 1.10-3 meq H+ /g for the TS-1 to a concentration of 0.5 meq H+ /g for the sample doped with aluminium).
This example illustrates how the acidity of TS-1 is influenced by the introduction of boron.
Operating exactly as in example 2, 40 g of boric acid dissolved in 35 g of KOH were added to the Ludox silica. The acidity of the final product is 0.8-1 meq H+ /g.
In this case, the simultaneous substitution by the boron and titanium is demonstrated by IR examination. Besides the Ti band at 950 cm-1, the characteristic band of boron in tetrahedral coordination is clearly visible at 920 cm-1.
5.8 g of allyl alcohol were added to a solution of tertiary butyl alcohol (80 cc) containing 64 g of a 6.3% hydrogen peroxide solution in anhydrous tertiary butyl alcohol. 2 g of TS-1 catalyst (2 mol % TiO2) were added to this mixture, and the resultant mixture was stirred at ambient temperature. After 12 hours the reaction mixture was filtered, and the solvent distilled off under vacuum.
The purified residue contained 8 g of glycerin with a yield of 86%.
TABLE 1 |
______________________________________ |
TS-1 Silicalite(a) |
Interplanar Interplanar |
2θ |
distance, Rel. 2θ |
distance, |
Rel. |
(CuK- α) |
d(A) Int.(b) |
(CuK- α) |
d(A) Int.(b) |
______________________________________ |
7.94 11.14 vs 7.94 11.14 vs |
8.85 9.99 s 8.85 9.99 s |
9.08 9.74 m 9.08 9.74 m |
13.21 6.702 w 13.24 6.687 w |
13.92 6.362 mw 13.95 6.348 mw |
14.78 5.993 mw 14.78 5.993 mw |
15.55 5.698 w 15.55 5.698 w* |
15.90 5.574 w 15.90 5.574 w |
17.65 5.025 w 17.65 5.025 w |
17.81 4.980 w 17.83 4.975 w |
20.37 4.360 w 20.39 4.355 w |
20.85 4.260 mw 20.87 4.256 mw |
23.07 3.855 s 23.08 3.853 s |
23.28 3.821 ms |
23.29 3.819 s |
23.37 3.806 ms |
23.71 3.753 ms |
23.72 3.751 s |
23.80 3.739 ms |
23.92 3.720 s 23.94 3.717 s |
24.35 3.655 mw |
24.41 3.646 m |
24.60 3.619 mw |
25.84 3.448 w |
25.87 3.444 w |
25.97 3.431 w |
26.87 3.318 w* 26.95 3.308 w* |
29.23 3.055 w |
29.27 3.051 mw |
29.45 3.033 w |
29.90 2.988 mw 29.90 2.988 mw |
30.34 2.946 w 30.25 2.954 w |
45.00 2.014 mw* 45.05 2.012 mw* |
45.49 1.994 mw* 45.60 1.989 mw* |
______________________________________ |
(a) prepared by the method of U.S. Pat. No. 4,061,724. Product |
calcined at 550°C |
(b) vs: very strong; s: strong; ms: medium strong; m: medium; mw: |
medium weak; w: weak; *: multiplet |
TABLE 2 |
__________________________________________________________________________ |
EXAMPLE 3 4 5 6 7 |
__________________________________________________________________________ |
SiO2 /TiO2 (reagents) |
133 66 33 5 5 |
RN+ SiO2 (reagents) |
0.21 0.21 0.22 0.89 2 |
x (chemical analysis) |
0.005 0.008 0.012 0.017 0.023 |
Int.(950 cm-1)/Int.(800 cm-1) |
0.15 0.21 0.35 0.61 0.80 |
Elementary |
a, A 20.102(3) |
20.121(4) |
20.126(3) |
20.126(6) |
20.133(5) |
cell b, A 19.896(12) |
19.900(4) |
19.902(3) |
19.923(4) |
19.933(3) |
constants(a) |
c, A 13.373(3) |
13.373(3) |
13.393(3) |
13.410(3) |
13.416(3) |
α, ° |
90.46(1) |
90.58(1) |
Elementary cell volume V, A3 |
5348.5 5354.3 5364.7 5376.7 5384.0 |
__________________________________________________________________________ |
(a) The standard deviations referring to the last figure given are |
shown in parentheses. When the value of α is not indicated, this |
signifies orthorhombic symmetry. The elementary cell constants for the |
pure silicalite are: |
a = 20.117(5) ; b = 19.874(5) ; c = 13.371(4) A; α = |
90.62(1) °; V = 5345.5 A3. |
Notari, Bruno, Taramasso, Marco, Perego, Giovanni
Patent | Priority | Assignee | Title |
10053439, | Jul 24 2013 | BASF SE; Dow Global Technologies LLC | Catalyst system for preparing propylene oxide |
10100024, | Jul 29 2014 | Evonik Operations GmbH | Process for the epoxidation of an olefin |
10125108, | Apr 28 2015 | Evonik Operations GmbH | Process for the epoxidation of propene |
10173954, | Feb 17 2012 | Rhodia Operations; CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE—C.N.R.S. | Process for hydroxylation of aromatic compounds, hydroxylation catalyst and process for preparing same |
10179753, | Oct 21 2015 | EXELUS, INC | Process of making olefins or alkylate by reaction of methanol and/or DME or by reaction of methanol and/or DME and butane |
10207925, | Aug 27 2014 | Diehl Aviation Gilching GmbH | Zeolite components for use in solid chemical oxygen generators |
10213771, | Nov 09 2015 | China Petroleum & Chemical Corporation; SHANGHAI RESEARCH INSTITUTE OF PETROCHEMICAL TECHNOLOGY, SINOPEC | SCM-11 molecular sieve, process for producing same and use thereof |
10265686, | Jul 05 2013 | DANMARKS TEKNISKE UNIVERSITET | Method of producing zeolite encapsulated nanoparticles |
10266416, | Jul 05 2013 | DANMARKS TEKNISKE UNIVERSITET | Method for producing zeolites and zeotypes |
10266417, | Apr 24 2012 | BASF SE | Zeolitic materials and methods for their preparation using alkenyltrialkylammonium compounds |
10338287, | Aug 29 2017 | SOUTHWALL TECHNOLOGIES INC | Infrared-rejecting optical products having pigmented coatings |
10343151, | Nov 09 2015 | China Petroleum & Chemical Corporation; SHANGHAI RESEARCH INSTITUTE OF PETROCHEMICAL TECHNOLOGY, SINOPEC | Process for producing a molecular sieve having the SFE structure, molecular sieve having the SFE structure and use thereof |
10399068, | Nov 09 2015 | China Petroleum & Chemical Corporation; SHANGHAI RESEARCH INSTITUTE OF PETROCHEMICAL TECHNOLOGY, SINOPEC | SCM-10 molecular sieve, process for producing same and use thereof |
10493440, | Mar 10 2015 | California Institute of Technology | Methods to produce molecular sieves with LTA topology and compositions derived therefrom |
10613261, | Apr 09 2018 | SOUTHWALL TECHNOLOGIES INC | Selective light-blocking optical products having a neutral reflection |
10627555, | Apr 09 2018 | SOUTHWALL TECHNOLOGIES INC | Selective light-blocking optical products having a neutral reflection |
10662126, | Oct 21 2015 | Exelus, Inc. | Process of making olefins or alkylate by reaction of methanol and/or DME or by reaction of methanol and/or DME and butane |
10730756, | Apr 19 2004 | Ecolab USA Inc. | Colloidal compositions and methods of preparing same |
10974967, | Jun 13 2017 | China Petroleum & Chemical Corporation; SHANGHAI RESEARCH INSTITUTE OF PETROCHEMICAL TECHNOLOGY, SINOPEC | Molecular sieve SCM-15, synthesis method therefor and use thereof |
10995008, | Mar 30 2016 | BASF SE | Process for the flash calcination of a zeolitic material |
11097256, | Jun 13 2017 | China Petroleum & Chemical Corporation; SHANGHAI RESEARCH INSTITUTE OF PETROCHEMICAL TECHNOLOGY, SINOPEC | Molecular sieve SCM-14, a preparation process and use thereof |
11192794, | Dec 07 2017 | Evonik Operations GmbH | Production of pulverulent, porous crystalline metal silicates by means of flame spray pyrolysis |
11434146, | Jan 09 2017 | Evonik Operations GmbH | Method for producing metal oxides by means of spray pyrolysis |
11492307, | Oct 21 2015 | Exelus Inc. | Process of making olefins or alkylate by reaction of methanol and/or DME or by reaction of methanol and/or DME and butane |
11542170, | Mar 30 2016 | BASF SE | Process for the flash calcination of a zeolitic material |
11747532, | Sep 15 2017 | SOUTHWALL TECHNOLOGIES INC | Laminated optical products and methods of making them |
4519998, | Aug 26 1982 | Centre de Recherche Industrielle du Quebec | Process for the preparation of a crystalline titanoborosilicate |
4547557, | Jul 09 1984 | Phillips Petroleum Company | Silica-titania cogel from two-step hydrolysis |
4623526, | Aug 26 1982 | Centre de Recherche Industrielle du Quebec | Process for the preparation of a crystalline titanoborosilicate |
4656016, | Jun 22 1978 | Snamprogetti, S.p.A. | Silica-based synthetic materials containing boron in the crystal lattice and processes for their preparation |
4683050, | Oct 15 1979 | UOP | Mild hydrocracking with a catalyst containing an intermediate pore molecular sieve |
4686029, | Dec 06 1985 | UOP, DES PLAINES, IL , A NY GENERAL PARTNERSHIP; KATALISTIKS INTERNATIONAL, INC | Dewaxing catalysts and processes employing titanoaluminosilicate molecular sieves |
4701428, | Apr 23 1985 | ENICHEM SINTESI S P A | Catalyst of silicon and titanium having high mechanical strength and a process for its preparation. |
4705675, | Nov 16 1984 | The Standard Oil Company | Synthesis of molecular sieving metallosilicates using silica-transition metal oxide sols |
4707345, | Apr 26 1984 | UOP, DES PLAINES, IL , A NY GENERAL PARTNERSHIP; KATALISTIKS INTERNATIONAL, INC | Titanium-aluminum-silicon-oxide molecular sieve compositions and process for preparing the same |
4708857, | Jul 26 1983 | Centre de Recherche Industrielle du Quebec | Process for preparing a crystalline iron-borosilicate |
4711869, | Nov 08 1985 | BASF Corporation | Silica-titania hydrocarbon conversion catalyst |
4788380, | Apr 26 1984 | UOP, DES PLAINES, ILLINOIS A NY GENERAL PARTNERSHIP; KATALISTIKS INTERNATIONAL, INC | Titanium-aluminum-silicon-oxide molecular sieve compositions |
4824976, | Jan 28 1986 | The Dow Chemical Company | Process for the epoxidation of olefinic compounds and catalysts used therein |
4828812, | Dec 29 1987 | Mobil Oil Corporation | Titanosilicates of enhanced ion exchange capacity and their preparation |
4829040, | Oct 15 1979 | UOP | Catalyst containing an intermediate pore molecular sieve for mild hydrocracking |
4859785, | Apr 23 1985 | Enichem Sintesi S.p.A. | Catalyst on the basis of silicon and titanium having high mechanical strength |
4869805, | Apr 16 1984 | UOP, DES PLAINES, ILLINOIS A NY GENERAL PARTNERSHIP; KATALISTIKS INTERNATIONAL, INC | Titanium-aluminum-silicon-oxide molecular sieve compositions |
4892720, | Apr 26 1984 | UOP, DES PLAINES, ILLINOIS A NY GENERAL PARTNERSHIP; KATALISTIKS INTERNATIONAL, INC | Substituted aluminosilicate compositions and process for preparing same |
4918194, | Oct 29 1987 | MONTEDIPE S P A | Process for the synthesis of a N,N-dialkyl-hydroxylamine |
4954653, | Apr 23 1985 | Enichem Sintesi S.p.A. | Catalyst on the basis of silicon and titanium having high mechanical strength and a process for its preparation |
4996385, | Nov 08 1985 | Aristech Chemical Corporation | Use of silica-titania hydrocarbon conversion catalyst in hydrocarbon conversion processes |
5015453, | Apr 28 1989 | W. R. Grace & Co.-Conn. | Crystalline group IVA metal-containing molecular sieve compositions |
5063037, | Sep 24 1986 | Mobil Oil Corp. | Crystalline borosilicate |
5064629, | Apr 06 1988 | MAKIKO ASAOKA | Titanium-boron-oxide, synthetic materials based thereon and method of preparing the same |
5082641, | May 22 1987 | RHONE-POULENC CHIMIE, 25, QUAI PAUL DOUMER - 92408 - COURBEVOIE, FRANCE | Silicon/titanium oxide MFI zeolites |
5098687, | Apr 26 1984 | UOP | Substituted aluminosilicate compositions and process for preparing same |
5143886, | Feb 07 1990 | SNAMPROGETTI S P A | Catalytic composition for the dehydrogenation of C2 -C5 paraffins |
5160717, | Apr 26 1984 | UOP, A CO OF NY | Titanium-aluminum-silicon-oxide molecular sieve compositions |
5214168, | Apr 30 1992 | ARCO CHEMICAL TECHNOLOGY, L P | Integrated process for epoxide production |
5221795, | Aug 02 1991 | ENIRICERCHE S P A | Process for producing olefin oxides |
5233097, | Oct 15 1992 | UOP | Oxidation of aromatics to hydroxyaromatics using aluminosilicates containing framework titanium |
5252758, | Nov 26 1991 | ENIRICERCHE S P A | Process for oxidizing organic compounds |
5262550, | Apr 30 1992 | ARCO CHEMICAL TECHNOLOGY, L P | Epoxidation process using titanium-rich silicalite catalysts |
5271761, | Apr 26 1984 | UOP | Substituted aluminosilicate compositions and process for preparing |
5290533, | Dec 19 1985 | Eniricerche S.p.A.; Enichem Synthesis S.p.A.; Snamprogetti S.p.A. | Method for production of a coated substrate with controlled surface characteristics |
5332830, | Apr 30 1992 | BASF Aktiengesellschaft | Preparation of N-hydroxyazoles |
5354875, | Dec 23 1993 | UOP | Epoxidation of olefins using a titania-supported titanosilicate |
5401486, | Nov 21 1991 | BASF Aktiengesellschaft | Preparation of essentially alkali-free titanium zeolites |
5412122, | Dec 23 1993 | ARCO CHEMICAL TECHNOLOGY, L P | Epoxidation process |
5434118, | Dec 21 1990 | Eniricerche S.p.A.; Snamprogetti SpA | Catalytically active gel and a process for its preparation |
5453511, | Sep 08 1994 | Arco Chemical Technology, L.P. | Bis-piperidinium compounds |
5466835, | Dec 23 1993 | UOP | Titanosilicate as an epoxidation catalyst for olefins |
5466869, | Oct 31 1994 | Hoechst Celanese Corporation; Delft University of Technology | Process for perparing 4-hydroxyacetophenone oxime |
5474754, | Aug 15 1994 | LYONDELL CHEMICAL TECHNOLOGY, L P | Preparation of an aluminosilicotitanate isomorphous with zeolite beta |
5527520, | Sep 08 1994 | LYONDELL CHEMICAL TECHNOLOGY, L P | Method of making a titanium-containing molecular sieve |
5536857, | Jul 05 1994 | Visteon Global Technologies, Inc | Single source volatile precursor for SiO2.TiO2 powders and films |
5573989, | Aug 06 1993 | Sumitomo Chemical Company, Limited | Process for producing olefin oxides |
5578744, | Dec 21 1990 | Eniricerche S.p.A.; Snamprogetti S.p.A. | Catalytically active gel and a process for its preparation |
5582819, | Feb 24 1995 | DAELIM INDUSTRIAL CO , LTD | Fibrous zeolite and preparation method thereof |
5618512, | Nov 30 1995 | ARCO CHEMICAL TECHNOLOGY, L P | Niobium-containing zeolites |
5621122, | Sep 08 1994 | LYONDELL CHEMICAL TECHNOLOGY, L P | Epoxidation process |
5639880, | May 30 1996 | BASF Aktiengesellschaft | Preparation of amine oxides |
5648562, | Aug 03 1994 | Sandoz Ltd. | Oxidation process |
5656252, | Jan 28 1994 | Elf Aquitaine Production | Process for obtaining zeolites containing titanium |
5679749, | Nov 30 1995 | LYONDELL CHEMICAL TECHNOLOGY, L P | Olefin epoxidation using niobium-containing zeolites |
5681789, | Feb 12 1996 | LYONDELL CHEMICAL TECHNOLOGY, L P | Activation of as-synthesized titanium-containing zeolites |
5683952, | Aug 11 1993 | Mitsubishi Gas Chemical Company, Inc. | Titanosilicate catalyst particle |
5684170, | Dec 23 1993 | LYONDELL CHEMICAL TECHNOLOGY, L P | Epoxidation process |
5688484, | Jul 29 1996 | LYONDELL CHEMICAL TECHNOLOGY, L P | Non-hydrothermal method of making a titanium-containing zeolite |
5688975, | Apr 10 1996 | UOP | Rare earth stabilized Cr/Ti substituted molecular sieves |
5691266, | Aug 11 1993 | Mitsubishi Gas Chemical Company, Inc. | Method of making a titanosilicate catalyst |
5695736, | Dec 23 1993 | LYONDELL CHEMICAL TECHNOLOGY, L P | Tiatanium containing molecular sieve having a zelite beta structure |
5712402, | Dec 14 1994 | Board of Trustees Operating Michigan State University | Catalytic applications of mesoporous metallosilicate molecular sieves and methods for their preparation |
5736479, | Dec 03 1992 | Leuna-Katalysatoren GmbH | Oxidation catalysts |
5744619, | Mar 17 1997 | UOP LLC | Titanovanadosilicalites as epoxidation catalysts for olefins |
5780654, | Apr 22 1997 | UOP LLC | Titanostannosilicalites: epoxidation of olefins |
5783167, | Jun 15 1993 | Consejo Superior Investigaciones Cientificas; Universidad Politecnica Valencia | Structure material of the zeolite type with ultralarge pores and a lattice comprised of silicone and titanium oxides: its synthesis and utilization for the selective oxidation of organic products |
5795555, | Nov 24 1994 | Council of Scientific & Industrial Research | Micro-meso porous amorphous titanium silicates and a process for preparing the same |
5855864, | Aug 22 1994 | Board of Trustees Operating Michigan State University | Catalytic applications of mesoporous metallosilicate molecular sieves and methods for their preparation |
5869706, | Mar 06 1996 | California Institute of Technology | Epoxidation process using a synthetic crystalline material oxides of silicon and titanium |
5874596, | Aug 11 1993 | Mitsubishi Gas Chemical Company, Inc. | Titanosilicate catalyst particle |
5882624, | Jan 29 1997 | Englehard Corporation; Engelhard Corporation | ETS-14 crystalline titanium silicate molecular sieves, manufacture and use thereof |
5885546, | Dec 09 1994 | Council of Scientific & Industrial Research | Process for the preparation of titanium silicates |
5888471, | Oct 22 1986 | Eniricerche S.p.A.; Enichem Synthesis S.p.A.; Snamprogetti | Synthetic crystalline porous material containing oxides of silicon, titanium and gallium |
5958369, | May 30 1997 | Director-General of Agency of Industrial Science and Technology | Titanium-containing porous silica and process of preparing same |
5968474, | Sep 30 1994 | Chevron U.S.A. Inc. | Pure phase titanium-containing zeolite having MEL structure, process for preparing same, and oxidation processes using same as catalyst |
5973171, | Oct 07 1998 | LYONDELL CHEMICAL TECHNOLOGY, L P | Propylene oxide production |
5977009, | Apr 02 1997 | Arco Chemical Technology, LP; ARCO CHEMICAL TECHNOLOGY, L P | Catalyst compositions derived from titanium-containing molecule sieves |
6005123, | Apr 16 1998 | LYONDELL CHEMICAL TECHNOLOGY, L P | Epoxidation process |
6008388, | Apr 16 1998 | LYONDELL CHEMICAL TECHNOLOGY, L P | Epoxidation process |
6031116, | Jul 01 1996 | Dow Global Technologies LLC | Process for the direct oxidation of olefins to olefin oxides |
6042807, | Apr 02 1997 | Arco Chemical Technology, L.P.; ARCO CHEMICAL TECHNOLOGY, L P | Tellurium-containing molecular sieves |
6054112, | Oct 25 1996 | Evonik Degussa GmbH | Process for the preparation of titanium containing molecular sieves |
6074622, | Oct 11 1996 | Elf Atochem S.A. | Catalyst based on titanosilicalites and process for producing N,N-disubstituted hydroxylamine |
6074624, | Apr 22 1997 | UOP LLC | Titanostannosilicates and preparation thereof |
6083864, | Oct 22 1986 | Eniricerche S.p.A. | Synthetic, crystalline, porous material containing oxides of silicon, titanium and gallium |
6106803, | Jul 23 1997 | Evonik Degussa GmbH | Granulates which contain titanium silicalite-1 |
6127307, | Mar 05 1996 | BASF Aktiengesellschaft | Catalyst composition free from noble metals |
6133487, | Nov 27 1997 | Enichem S.p.A. | Process for the oxidation of aromatic compounds to hydroxyaromatic compounds |
6139721, | Mar 24 1997 | AGIP PETROLI S P A | Fluid bed catalytic cracking process characterized by a high selectivity to olefins |
6160138, | Mar 26 1998 | Repsol Quimica, S.A. | Process for epoxydation of olefinic compounds with hydrogen peroxide |
6193943, | Aug 22 1994 | Board of Trustees Operating Michigan State University | Catalytic applications of mesoporous metallosilicate molecular sieves and methods for their preparation |
6194591, | Apr 27 2000 | LYONDELL CHEMICAL TECHNOLOGY, L P | Aqueous epoxidation process using modified titanium zeolite |
6255499, | Apr 08 1999 | Dow Global Technologies LLC | Process for the hydro-oxidation of olefins to olefin oxides using oxidized gold catalyst |
6307073, | Jul 25 2000 | LYONDELL CHEMICAL TECHNOLOGY, L P | Direct epoxidation process using a mixed catalyst system |
6309998, | Jul 01 1996 | The Dow Chemical Company | Process for the direct oxidation of olefins to olefin oxides |
6323351, | Dec 09 1999 | Dow Global Technologies Inc | Process for the direct oxidation of olefins to olefin oxides |
6325946, | Jun 02 2000 | Degussa AG | Process for treating waste water |
6329537, | Apr 02 1997 | Arco Chemical Technology, L.P. | Tellurium-containing molecular sieves |
6387349, | Mar 26 2001 | Council of Scientific and Industrial Research | Process for the microwave induced preparation of crystalline microporous titanium silicalite |
6391278, | Aug 22 1994 | Board of Trustees Operating Michigan State University | Catalytic applications of mesoporous metallosilicate molecular sieves and methods for their preparation |
6391279, | Nov 14 1997 | LANTHEUS MEDICAL IMAGING, INC | Radioactive seeds for brachytherapy and a process for making the same |
6399794, | Nov 15 2001 | LYONDELL CHEMICAL TECHNOLOGY, L P | Direct epoxidation process using carbonate modifiers |
6403815, | Nov 29 2001 | LYONDELL CHEMICAL TECHNOLOGY, L P | Direct epoxidation process using a mixed catalyst system |
6413902, | Aug 22 1994 | BOARD OF TRUSTEES OF MICHIGAN STATE UNIVERSITY | Catalytic applications of mesoporous metallosilicate molecular sieves and methods for their preparation |
6475465, | Dec 24 1999 | China Petrochemical Corporation; RESEARCH INSTITUTE OF PETROLEUM PROCESSING, SINOPEC | Titanium-silicalite molecular sieve and the method for its preparation |
6476275, | Sep 25 2000 | Haldor Topsoe A/S | Process for the catalytic selective oxidation of a hydrocarbon compound in presence of mesoporous zeolite |
6479711, | Apr 28 1999 | Mitsui Chemicals, Inc. | Process for producing aromatic hydroxy compound |
6504040, | Dec 11 1998 | Bayer Aktiengesellschaft | Integrated method for producing epoxides from olefins |
6521808, | Feb 17 2000 | Ohio State Innovation Foundation | Preparation and use of a catalyst for the oxidative dehydrogenation of lower alkanes |
6524984, | Oct 03 1997 | ENICHEM S P A | Process for preparing bound zeolites |
6524991, | Jul 01 1996 | Dow Global Technologies LLC | Process for the direct oxidation of olefins to olefin oxides |
6562986, | Jun 30 1997 | Dow Global Technologies, Inc. | Process for the direct oxidation of olefins to olefin oxides |
6596881, | Jun 13 2001 | Evonik Degussa GmbH | Process for the epoxidation of olefins |
6596883, | Aug 23 2001 | Thyssenkrupp Uhde GmbH | Process for the epoxidation of olefins |
6600055, | Jun 13 2001 | Evonik Degussa GmbH | Process for the epoxidation of olefins |
6603028, | Aug 07 1998 | Bayer Aktiengesellschaft | Method for oxidizing hydrocarbons |
6608219, | Jun 13 2001 | Evonik Operations GmbH | Process for the epoxidation of olefins |
6610865, | Aug 15 2001 | Evonik Operations GmbH | Process for the epoxidation of olefins |
6617465, | Jan 08 2001 | Thyssenkrupp Uhde GmbH | Process for the epoxidation of olefins |
6624319, | Feb 07 2000 | Evonik Degussa GmbH | Process for the epoxidation of olefins |
6627175, | Feb 17 2000 | SOLVAY SOCIETE ANONYME | Process for the manufacture of a crystalline solid |
6646141, | Feb 07 2000 | Evonik Operations GmbH | Process for the epoxidation of olefins |
6646142, | Dec 16 1998 | Dow Global Technologies Inc | Process for the direct oxidation of olefins to olefin oxides |
6669924, | Nov 23 1999 | Universite Laval | Mesoporous zeolitic material with microporous crystalline mesopore walls |
6670491, | Jun 30 1997 | Dow Global Technologies Inc. | Process for the direct oxidation of olefins to olefin oxides |
6670492, | Feb 07 2000 | Evonik Operations GmbH | Process for the expoxidation of olefins |
6720436, | Mar 18 2002 | Evonik Degussa GmbH | Process for the epoxidation of olefins |
6749668, | Jun 18 2001 | Evonik Degussa GmbH | Process for the recovery of combustible components of a gas stream |
6753287, | Apr 23 1999 | Bayer Aktiengesellschaft | Sol-gel hybrid materials containing precious metals as catalysts for partial oxidation of hydrocarbons |
6805851, | Aug 20 1999 | BASF Aktiengesellschaft | Method for producing crystalline, zeolitic solid matter |
6838572, | Sep 30 2002 | Evonik Degussa GmbH | Process for the epoxidation of olefins |
6841144, | Mar 02 2000 | Evonik Degussa GmbH | Method for the production of a titanium-containing zeolite |
6846406, | Oct 11 2000 | Consejo Superior de Investigaciones Cientificas; Universidad Politecnica de Valencia | Process and catalysts for eliminating sulphur compounds from the gasoline fraction |
6884743, | Sep 16 2002 | BASF Aktiengesellschaft | Catalyst for epoxidation reactions |
6958405, | Mar 09 2004 | LYONDELL CHEMICAL TECHNOLOGY, L P | Polymer-encapsulated titanium zeolites for oxidation reactions |
6960671, | Sep 20 2002 | LYONDELL CHEMICAL TECHNOLOGY, L P | Process for direct oxidation of propylene to propylene oxide and large particle size titanium silicalite catalysts for use therein |
6972337, | Aug 12 2004 | LYONDELL CHEMICAL TECHNOLOGY, L P | Epoxidation catalyst |
6984606, | Feb 19 2004 | LYONDELL CHEMICAL TECHNOLOGY, L P | Epoxidation catalyst |
7018595, | Oct 03 1997 | Enichem S.p.A. | Process for preparing bound zeolites |
7026492, | Oct 29 2004 | LYONDELL CHEMICAL TECHNOLOGY, L P | Direct epoxidation process using modifiers |
7030255, | Mar 09 2004 | LYONDELL CHEMICAL TECHNOLOGY, L P | Oxidation process with in-situ H202 generation and polymer-encapsulated catalysts therefor |
7057056, | Dec 17 2004 | LYONDELL CHEMICAL TECHNOLOGY, L P | Epoxidation catalyst |
7074383, | Oct 03 1997 | Enichem S.p.A. | Process for preparing bound zeolites |
7081237, | Aug 20 1999 | BASF Aktiengesellschaft | Preparation of a crystalline, zeolitic solid |
7091365, | Mar 08 2004 | ABB Lummus Global Inc. | Process for olefin epoxidation and co-production of nylon precursor |
7138534, | Aug 11 2000 | Dow Global Technologies LLC | Process for the continuous production of an olefinic oxide |
7141683, | May 02 2002 | Evonik Degussa GmbH | Process for the epoxidation of olefins |
7148381, | Jun 28 2001 | POLIMERI EUROPA S P A | Process for the activation of zeolitic catalysts containing titanium and their use in oxidation reactions |
7148386, | Jul 30 2004 | SHPP GLOBAL TECHNOLOGIES B V | Processes for preparing benzoquinones and hydroquinones |
7169945, | Nov 26 2002 | Evonik Degussa GmbH | Process for the epoxidation of olefins |
7193093, | Jun 30 2003 | Shell Oil Company | Process for producing alkylene oxide |
7232783, | Jul 02 2005 | Lyondell Chemical Technology, L.P. | Propylene oxide catalyst and use |
7235676, | Mar 31 2004 | Council of Scientific & Industrial Research | Catalytic process for the preparation of epoxides from alkenes |
7238817, | Feb 22 2006 | Lyondell Chemical Technology, L.P.; LYONDELL CHEMICAL TECHNOLOGY, L P | Direct epoxidation process |
7271117, | Jun 17 2004 | LYONDELL CHEMICAL TECHNOLOGY, L P | Epoxidation catalyst |
7273826, | Jul 26 2005 | Lyondell Chemical Technology, L.P. | Epoxidation catalyst |
7276464, | Jun 17 2004 | LYONDELL CHEMICAL TECHNOLOGY, L P | Titanium zeolite catalysts |
7288237, | Nov 17 2005 | Lyondell Chemical Technology, L.P. | Epoxidation catalyst |
7357909, | Jun 28 2006 | Lyondell Chemical Technology, L.P. | Process for producing hydrogen peroxide |
7371318, | Apr 12 2001 | Consejo Superior de Investigaciones Cientificas; UNIVESIDAD POLITECNICA DE VALENCIA | Method and catalysts for the elimination of sulphur compounds from the diesel fraction |
7381675, | Dec 19 2006 | Lyondell Chemical Technology, L.P.; LYONDELL CHEMICAL TECHNOLOGY, L P | Direct epoxidation catalyst |
7384882, | May 31 2002 | China Petroleum & Chemical Corporation | Process for regenerating titanium-containing catalysts |
7387981, | Jun 28 2007 | Lyondell Chemical Technology, L.P.; LYONDELL CHEMICAL TECHNOLOGY, L P | Direct epoxidation catalyst and process |
7399726, | Sep 20 2002 | LYONDELL CHEMICAL TECHNOLOGY, L P | Process for direct oxidation of propylene to propylene oxide and large particle size titanium silicalite catalysts for use therein |
7408080, | May 31 2002 | China Petroleum & Chemical Corporation; RESEARCH INSTITUTE OF PETROLEUM PROCESSING, SINOPEC | Process for ammoximation of carbonyl compounds |
7432384, | Oct 25 2005 | Lyondell Chemical Technology, L.P. | Direct epoxidation process |
7432402, | Dec 28 2005 | CHEVRON U S A INC | Partial oxidation using molecular sieve SSZ-74 |
7449600, | Feb 28 2005 | Sumitomo Chemical Company, Limited | Process for producing cyclohexanone oxime |
7453003, | Aug 29 2007 | Lyondell Chemical Technology, L.P. | Direct epoxidation catalyst and process |
7470800, | Jun 17 2004 | Lyondell Chemical Technology, L.P. | Titanium zeolite catalysts |
7470801, | Oct 24 2007 | Lyondell Chemical Technology, L.P.; LYONDELL CHEMICAL TECHNOLOGY, L P | Direct epoxidation process using a mixed catalyst system |
7476770, | Jul 26 2005 | Lyondell Chemical Technology, L.P. | Epoxidation catalyst |
7501532, | Nov 20 2007 | Lyondell Chemical Technology, L.P.; LYONDELL CHEMICAL TECHNOLOGY, L P | Process for producing hydrogen peroxide |
7531675, | Oct 24 2007 | Lyondell Chemical Technology, L.P.; LYONDELL CHEMCIAL TECHNOLOGY, L P | Direct epoxidation process using improved catalyst composition |
7563740, | Dec 19 2006 | LYONDELL CHEMICAL TECHNOLOGY, L P | Direct epoxidation process |
7595410, | Jul 18 2006 | LYONDELL CHEMICAL TECHNOLOGY, L P | Direct epoxidation process using improved catalyst composition |
7615654, | Oct 20 2005 | Lyondell Chemical Technology, L.P.; LYONDEL CHEMICAL TECHNOLOGY, L P | Direct epoxidation process |
7648936, | Jan 29 2008 | Lyondell Chemical Technology, L.P. | Spray-dried transition metal zeolite and its use |
7671222, | Jul 12 2006 | Lyondell Chemical Technology, L.P.; LYONDELL CHEMICAL TECHNOLOGY, L P | Direct epoxidation process using a mixed catalyst system |
7696367, | Apr 10 2007 | LYONDELL CHEMICAL TECHNOLOGY, L P | Direct epoxidation process using a mixed catalyst system |
7713906, | Jun 21 2001 | Shell Oil Company | Catalyst composition, process for its preparation and use thereof |
7722847, | Sep 30 2002 | Evonik Operations GmbH | Aqueous hydrogen peroxide solutions and method of making same |
7767835, | Dec 18 2008 | Lyondell Chemical Technology, L.P.; LYONDELL CHEMICAL TECHNOLOGY, L P | Direct epoxidation process using improved catalyst |
7786318, | Apr 12 2005 | LYONDELL CHEMICAL TECHNOLOGY, L P | Catalyst preparation |
7825204, | Dec 19 2006 | LyondellBasell Acetyls, LLC | Inorganic oxide extrudates |
7837977, | Sep 13 2005 | CHEVRON U S A INC | Preparation of titanosilicate zeolite TS-1 |
7838455, | Jul 27 2005 | SK INNOVATION CO , LTD | Method of regeneration of titanium-containing molecular sieve catalyst |
7855304, | Dec 19 2006 | LyondellBasell Acetyls, LLC | Inorganic oxide extrudates |
7956204, | Sep 13 2005 | Chevron U.S.A. Inc. | Process for the oxidation of hydrocarbons utilizing shaped binderless TS-1 zeolite catalyst |
7973184, | Mar 13 2009 | TOKYO METROPOLITAN PUBLIC UNIVERSITY CORPORATION | Method for producing propylene oxide |
7981391, | Sep 30 2002 | Evonik Degussa GmbH | Aqueous hydrogen peroxide solutions and method of making same |
8003825, | Apr 25 2005 | Sumitomo Chemical Company, Limited | Process for producing cycloalkanone oximes |
8119550, | Sep 16 2003 | BASF Aktiengesellschaft | Process for epoxidation and catalyst to be used therein |
8124797, | Jun 26 2009 | LYONDELL CHEMICAL TECHNOLOGY, L P | Epoxidation process |
8124798, | Dec 17 2009 | LYONDELL CHEMICAL TECHNOLOGY, L P | Direct epoxidation catalyst and process |
8198479, | Feb 17 2005 | MONSANTO TECHNOLOGY LLC | Transition metal-containing catalysts and catalyst combinations including transition metal-containing catalysts and processes for their preparation and use as oxidation catalysts |
8449812, | Mar 29 2000 | Evonik Operations GmbH | Process for the production of a titanium silicalite shaped article |
8540956, | Dec 11 2009 | China Petrochemical Development Corporation | Method for preparing titanium-silicalite molecular sieve and method for preparing cyclohexanone oxime using titanium-silicalite molecular sieve |
8545608, | Jun 28 2006 | The Governors of the University of Alberta | Silicate materials, method for their manufacture, and method for using such silicate materials for adsorptive fluid separations |
8703983, | Mar 25 2010 | Blue Cube IP LLC | Process for producing propylene oxide using a pretreated epoxidation catalyst |
8729256, | Jan 15 2010 | California Institute of Technology | Isomerization of sugars |
8735612, | Mar 25 2010 | Blue Cube IP LLC | Pretreated epoxidation catalyst and a process for producing an olefin therewith |
8753998, | Apr 19 2011 | China Petrochemical Development Corporation, Taipei (Taiwan) | Method for preparing titanium-silicalite molecular sieve and method for preparing cyclohexanone oxime using the molecular sieve |
8772192, | Jun 29 2012 | Saudi Basic Industries Corporation | Germanium silicalite catalyst and method of preparation and use |
8772194, | Feb 14 2011 | China Petrochemical Development Corporation, Taipei (Taiwan) | Method for preparing large-sized titanium-silicalite molecular sieve and method for preparing cyclohexanone oxime using the molecular sieve |
8790608, | Sep 12 2008 | Ecolab USA Inc | Siliceous materials having tunable porosity and surface morphology and methods of synthesizing same |
8962513, | Feb 17 2005 | MONSANTO TECHNOLOGY LLC | Transition metal-containing catalysts and catalyst combinations including transition metal-containing catalysts and processes for their preparation and use as oxidation catalysts |
8981132, | Mar 25 2010 | Blue Cube IP LLC | Pretreated epoxidation catalyst and a process for producing an olefin therewith |
9133106, | Dec 25 2012 | China Petrochemical Development Corporation | Method for producing ketoxime |
9221038, | Nov 13 2008 | SUED-CHEMIE IP GMBH & CO KG | Metal-containing crystalline silicates |
9255120, | Apr 11 2013 | California Institute of Technology | Conversion of glucose to sorbose |
9358531, | Dec 14 2007 | POLIMERI EUROPA S P A | Process for the preparation of TS-1 zeolites |
9387505, | Sep 17 2012 | Eastman Chemical Company | Methods, materials and apparatus for improving control and efficiency of layer-by-layer processes |
9393589, | Feb 15 2011 | Eastman Chemical Company | Methods and materials for functional polyionic species and deposition thereof |
9395475, | Oct 07 2011 | Eastman Chemical Company | Broadband solar control film |
9453949, | Dec 15 2014 | Eastman Chemical Company | Electromagnetic energy-absorbing optical product and method for making |
9475041, | Apr 24 2012 | BASF SE | Zeolitic materials and methods for their preparation using alkenyltrialkylammonium compounds |
9481583, | Oct 07 2011 | Eastman Chemical Company | Synthesis of metal oxide, titania nanoparticle product, and mixed metal oxide solutions |
9486790, | Oct 31 2011 | DALIAN UNIVERSITY OF TECHNOLOGY | Modification method of titanium-silicalite zeolite based on the mixture of quaternary ammonium salt and inorganic alkali |
9540298, | Sep 20 2013 | Mitsui Chemicals, Inc | Process for producing aromatic dihydroxy compound |
9656251, | Oct 29 2013 | China Petroleum & Chemical Corporation; RESEARCH INSTITUTE OF PETROLEUM PROCESSING, SINOPEC | Full-Si molecular sieve and its synthesis process |
9682909, | Feb 17 2012 | Rhodia Operations; CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE—CNRS | Process for hydroxylation of aromatic compounds, hydroxylation catalyst and process for preparing same |
9817166, | Dec 15 2014 | Eastman Chemical Company | Electromagnetic energy-absorbing optical product and method for making |
9891347, | Dec 15 2014 | Eastman Chemical Company | Electromagnetic energy-absorbing optical product and method for making |
9891357, | Dec 15 2014 | Eastman Chemical Company | Electromagnetic energy-absorbing optical product and method for making |
9896343, | Oct 29 2013 | China Petroleum & Chemical Corporation; RESEARCH INSTITUTE OF PETROLEUM PROCESSING, SINOPEC | Titanium silicalite molecular sieve and its synthesis |
Patent | Priority | Assignee | Title |
3329482, | |||
3941871, | Nov 02 1973 | Mobil Oil Corporation | Crystalline silicates and method of preparing the same |
3972983, | Nov 25 1974 | Mobil Oil Corporation | Crystalline zeolite ZSM-20 and method of preparing same |
4061724, | Sep 22 1975 | UOP, DES PLAINES, IL , A NY GENERAL PARTNERSHIP; KATALISTIKS INTERNATIONAL, INC | Crystalline silica |
4104294, | Nov 10 1977 | UOP, DES PLAINES, IL , A NY GENERAL PARTNERSHIP; KATALISTIKS INTERNATIONAL, INC | Crystalline silicates and method for preparing same |
4208305, | Dec 16 1976 | Shell Oil Company | Crystalline silicates and process of preparation |
4331641, | Nov 07 1979 | Equistar Chemicals, LP | Synthetic crystalline metal silicate compositions and preparation thereof |
Executed on | Assignor | Assignee | Conveyance | Frame | Reel | Doc |
Jun 29 1982 | Snamprogetti S.p.A. | (assignment on the face of the patent) | / |
Date | Maintenance Fee Events |
Apr 17 1987 | M170: Payment of Maintenance Fee, 4th Year, PL 96-517. |
Apr 20 1987 | ASPN: Payor Number Assigned. |
Apr 16 1991 | M171: Payment of Maintenance Fee, 8th Year, PL 96-517. |
Apr 03 1995 | M185: Payment of Maintenance Fee, 12th Year, Large Entity. |
Date | Maintenance Schedule |
Oct 18 1986 | 4 years fee payment window open |
Apr 18 1987 | 6 months grace period start (w surcharge) |
Oct 18 1987 | patent expiry (for year 4) |
Oct 18 1989 | 2 years to revive unintentionally abandoned end. (for year 4) |
Oct 18 1990 | 8 years fee payment window open |
Apr 18 1991 | 6 months grace period start (w surcharge) |
Oct 18 1991 | patent expiry (for year 8) |
Oct 18 1993 | 2 years to revive unintentionally abandoned end. (for year 8) |
Oct 18 1994 | 12 years fee payment window open |
Apr 18 1995 | 6 months grace period start (w surcharge) |
Oct 18 1995 | patent expiry (for year 12) |
Oct 18 1997 | 2 years to revive unintentionally abandoned end. (for year 12) |